Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 94/00520 PCI`/US~3/05790
21:1S9~3
AQUEOUS LIOUID FOF~ PRIMERS
FI~3LD OF l~E: INVENTION
S The present invention relates to aqueous liquid for primer~ which isapplied to improve surface of alkaline porous inorganic base materials such as
concrete, mortar and the like.
BACRGROUND OF T~ INVENTION
Because their surface layers are fragile, primers are usually applied on
the surface of inorganic cement building materials such as concrete, mortar,
slate and the like for the purpose of improving the surface reinforcement or
adhesive ~trength to paints for surface finish and the like. Heretofore, solventprimer liquid formed by dissolving synthetic resin into organic solvent has beenemployed as such primers. However, the solvent primer liquid is easy to ignite
because of its volatility and further it affects the human body when the fumes
are breathed. Thus, the above ~olvent primer liquid has many problems from the
viewpoints of safety, sanitation, and the like.
The present application has previously developed aqueous liquid for primers
wherein water is medium and organic solvent is not employed as medium, and has
already applied to the Japanese Patent Office (JPA 62-80694). And, also as a
further developed version, he developed one liquid type primer, which is formed
by copolymerizing dimethyl aminoalkylamide acrylate or epichlorohydrin adduct ofdimethyl aminoalkylamide methacrylate as a function group and alkoxysilane
element to be the aqueous resin superior in reinforcement effects of the surfacelayer of base materials by crosslinking irrespective of the alkaline degree of
base materials and already filed an application.
Although the above aqueous liquid can form a coat superior in waterproof
by crosslinking under both circumstances of acid and alkali, when the
~0 concentration of resin is raised, shelf stability deteriorates due to highviscosity. In addition, it has a defect that the permeability to inorganic
building material, reinforcinq ability to base materials and waterproof
properties deteriorate due to a rise of viscosity.
W O 94/00520 2 1 ~ 5 9 ~ ~ PCr/~S93/05790 ~
O~JECT OF T~E INVENTION
The object of the present invention is accordingly to provide aqueous ;~
liquid for primers superior in permeability and reinforcing ability to base
materials and waterproof properties by forming resin liquid in high concentration
and low viscosity without loss of crosslinking reaction.
SUMMARY OF T~E ~NVENTION
In the first aspect, this invention relates to the aqueous liquid for :.
primers, which contains a copolymer mainly formed with the following component
lO~A), (B) and (C) in aqueous medium, where (A) is a cationic monomer represented -;
as the following general formula (1)
R _
CH2= C CH
Z (CH2)n 1 --CH2 R
CH3 n
R: -H, -CH3, -C2 H5 or -C3 H7 ~ -
'~
Z: (CH2)m or. Il (CH2)--m '~.
O (1) '`
30 wherein Y i9 organic or inorganic monovalent anion; m is an integer O to 3 and
n is an integer 1 to 3. .
(B) is an alkoxysilane monomer represented as the following general
formula ( 2 ~ R
CH2= C
Z--Si (X)3 (2)
. :`
R: -H, -CH3. -C2Hs or -C3H7
Z: (CH2)--m or~(CH2)--m
~ O .
2 `~
W O 94/00520 PCT/US93/0~790
X: -OCH3. -OC2H5 or -OC2H4 OCH3 and 21 i i 9 3 tJ
(C) is an ethylenic unsaturated monomer; and wherein a structural unit
derived from the (A) component accounts for not less than 5% (by weight; the same
applies hereinafter) of the copolymer, a structural unit derived from the (8)
component accounts for not less than 0.5% of the copolymer and a structural uni~
derived from the ~C) component accounts for not more than 94.5% of the copolymer.
In addition, in the second aspect, the invention relates to the aqueous
liquid for primers which contains dispersedly a polymer found by polymerizing
ethylenic unsaturated monomer in the above aqueous liquid.
That is, the invention has performed a series of studies focused on water
soluble resin, especially acrylic resin, to find an aqueous liquid for primers,
which forms a strong coat having durability irrespective of types of base
materials (inorganic building materials) and furthermore is superior in
waterproof properties by forming high-concentrated and low viscous resin liquid.
He found out that, as a result, when special monomers (component A and component
B) represented a~ the above general formula (1) and (2), and an ethylenic
unsaturated monomer (component C) are polymerized at a specific ratio, a chain
polymer obtained shows a good solubility in water and furthermore the aqueous
solution penetrates the surface layer of base material very well so as to
reinforce the basic material surface strongly, and at the same time to form a
coat superior in waterproof and alkali resi3tance. Furthermore, he found out
that high concentrated and low viscous resin liquid was realized by
polymerization with cationic monomer represented as the above general formula
(1), without deteriorating the speed of crosslinking reaction compared with prior
methods, so that even in a coating condition of high concentration, permeability
to inorganic building materials remains favorable, and adequate reinforcement
toward basic materials and waterproof were given.
In addition, it was found out that similar effect was obtained in
polymerizing the above ethylenic unsaturated monomer solely by emulsion
polymerization and the like then mixing it with liquid of (A)+(B)+(C) which
contains a copolymer.
W 0 94/00520 2il~ `i,. PCT/US93/05790 ~
DETAI~ED DES~RIPTION OF THE PREFERRED EMBODIMENTS
In the pre~ent invention, water i6 the most preferably as medium. However,
for the purpose of heightening the solubility of a cationic monomer for
copolymerization or increasing the permeability to a basic material, it is
possible to use water jointly with organic solvent easily soluble in water at the
same time. And al~o, it is possible to u~e organic solvent only, easily soluble
in water. As such organic solvents, isopropyl alcohol, methanol, ethanol,
propanol, acetone, methyl ethyl ketone, dioxane, ethylene glycol, propylene
glycol, glycerin, methyl carbitol, ethyl carbitol, butyl carbitol, methyl
cellosolve, ethyl cellosolve, acetic acid, acetic acid esters of the above
alcohol, acetic acid esters of the above carbitol, acetic acid esters of the
above cellosolve and the like are available. In using such organic solvents
together at the same time, from the viewpoint of safety of aqueous liquid
obtained, it is preferable that a ratio of organic solvent in total medium is not
more than 50~ (by weight; the same applies hereinafter) and it is further
preferable that the ratio is not more than 20~. In using the above organic
solvents, it is possible to withdraw the organic solvents by distillation and the
like after finishing polymerization reaction.
Further, as a cationic monomer (component A) represented as the above
general formula (1), methyl chloride salt of dimethylaminopropyl methacrylamide,
acetate of dimethylaminopropyl methacrylamide, sulfate of dimethylaminopropyl
methacrylamide, nitrate of dimethylaminopropyl methacrylamide, formate of
dimethylaminopropyl methacrylamide, propionic acid salt of dimethylaminopropyl
methacrylamide, ethyl chloride salt of dimethylaminopropyl methacrylamide, methyl
bromide salt of dimethylaminopropyl methacrylamide, ethyl bromide salt of
dimethylaminopropyl methacrylamide, methyl iodide salt of dimethylaminopropyl
methacrylamide, methyl nitrate of dimethylaminopropyl dimethylacrylamide, ethyl
nitrate of dimethylaminopropyl dimethylacrylamide, dimethyl sulfate of
dimethylaminopropyl methacrylamide, diethyl sulfate of dimethylaminopropyl
methacrylamide, hydrochloride of dimethylaminopropyl methacrylamide, hydrobromic
acid salt of dimethylaminopropyl methacrylamide, hydroiodic acid salt of
dimethylaminopropyl methacrylamide are available.
It i8 required that the above cationic monomer should be compounded at a
ratio of not less than 5~ of total monomer (component A + component B + component
W094/00s20 P~/US93/05790
C). That is, when the ratio of cationic monomer is less than ~%~ ~he~3s~ngth
of the coat obtained and the adhesive strength with surface finish and adhesive
agent may not be adequate.
On the other hand, as an alkoxysilane monomer (B component) represented as
the above general formula (2), 3-metharyloxy propyl trimethoxysilane, vinyl
trimethoxysilane, vinyl triethoxysilane, vinyl trimethoxyethoxysilane, 3-meth-
acryloxypropyl triethoxysilane, vinyl tetramethylene trimethoxysilane, vinyl
octamethylene trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane are
available. It is required that the above alkoxysilane monomer should be
compounded at a ratio of not less than 0.5~ of total monomer (A component + B
component + C component). That is, when the ratio of alkoxysilane monomer is
less than 0.5~, the strength of the coat obtained and the adhesive strength and
glued connection with surface finish and adhesive agent may not be adequate, as
the same as the above cationic alkali crosslinkable monomer.
Furtbermore, as an ethylenic unsaturated monomer (C component)~ which can
be used together with the above A component and B component, hydrophobic monomers
such as vinyl acetate, alkyl acrylate esters, alkyl methacrylate esters, styrene,
acrylonitrile, methacrylonitrile are available. Either of sole use of these or
combination use of two or more will do. And also, in case of preparin~ a polymer
with the above ethylenic unsaturated monomer, hydrophilic monomers such as
acrylic acid, methacrylic acid, amides acrylate or methacrylate, methylol amides,
alkoxymethyl amides, alkyl amino esters, vinyl monochloroacetate, methyl
methacrylate, butyl acrylate, 2-ethyl hexyl acrylate and the like may be used
together with the above hydrophobic monomer at the same time. Either of sole use
or two or more will do in this case, too. Of course, the above hydrophilic
monomers should be used within a limit so that the produced polymer may not be
soluble in aqueous medium.
When the above ethylenic unsaturated monomers are copolymerized with the
above (A) component and (B) component, adhesive strength and glued connection
with basic material surface, surface finish paint, adhesive and the like will be
further improved. In this case, it i9 required that the above ethylenic
unsaturated monomer should be compounded at the ratio of not less than 94.5% of
the total monomer (A component + B component + C component).
i iJ ~i
WO 94/00520 PCl`/US93/05790
It is also possible to accomplish the invention by mixing the medium
containing a copolymer made from (A) + (B) + the above ethylenic unsaturated
monomer with a polymer (emulsion) made from the above ethylenic unsaturated
monomer, the same effect can be obtained. In this case, it is preferable that
a polymer (emulsion) (x) made from the ethylenic unsaturated monomer should be
compounded to the above medium containing a copolymer made from A component + B
component + C component at the ratio of X/Y = 0/100 to 90/lO.
Aqueous liquid for primers in the present invention can be made from the
above medium and each monomer, for example, in the following method. That is,
first of all, polymerization initiator is added into water, organic solvent, or
mixture of water and organic solvent as a polymerization medium, and then the ;
above cationic monomer, alkoxysilane monomer and ethylenic unsaturated monomer
are dropped to polymerize at the temperature of 60 to 90C over a period of 1 toS hours, as maintaining the chemical system in acid condition. If necessary,
chain transfer agent such as lauryl mercaptane, 2-mercaptoethanol and the like
should be added in advance to adjust molecular weight. And also, it is possible !,,
to add a variety of addition agents, for example, film making assistant, such as i~
butyl cellosolve, butyl carbitol, and acetate, antifoaming agent, pigment,
viscosity inhibitor and the like, should be added as necessity requires. Thus ~s~
Z0 the aqueous liquid for primers, which is the object, can be obtained.
In addition, in case of emulsion polymerizing the ethylenic unsaturated
monomer separately, publicly known prior method for emulsion polymerization is ;~`
available. And then emulsion obtained should be mixed with the medium containingthe above copolymer (a copolymer comprising A + B + the ethylenic unsaturated `~
monomer) so that aqueous liquid for primers as an object can be materialized. ;
Further, it is required to selectively use medium which does not inhibit
polymerization in the above method. As the above polymerization initiator, .
azobis isobutyronitrile, benzoyl peroxide (2,2'-azobis-amino-dipropane
i hydrochloride, ammonium persulfate and the like can be available. Furthermore,
it is important to maintain the above medium in acid condition because it
prevents chemical ~ystem from gelatinization. As acid for adjusting pH, organic
acid such as formic acid, acetic acid, oxalic acid and the like, and inorganic
acid such as hydrochloric acid, sulfuric acid, nitric acid and the like can be
available~
WO 94~00520 PCI/US93/05790
2~15~.93
Aqueous liquid for primers obtained in the above can be applied to surfaces
of inorganic basic materials such as concrete, mortar, slate plates, light weight
calcium plates, ALC plates and the like as primer. This coating liquid can
quickly penetrate the surface layer ~f basic materials as the medium penetrates,
and in a drying process, function group activated by alkali and water makes
crosslinking formation so that a strong coat of three dlmensional network
structure superior in waterproof and alkali resistance can be formed. As a
results, strong and durable reinforcement can be realized as strong as in the
case that solvent primer liquid is used.
Still furthermore, aqueous liquid for primers in the present invention is
superior from viewpoint of safety and public nuisance prevention without
volatilization of poisonous solvent because hydrophilic medium is adopted. Even
furthermore, since cation accounts for a portion of constitutional ingredients
of aqueous liquid in the present invention, affinity and adhesion to paint for
surface finish or adhesive agent, coated on the primer layer, are superior thanks
to the characteristic of cation, so that the surfac2 finish layer can be attached
strongly to the basic materials.
....
EXAMPLE 1 - ~, COMPARAT~VE EXAMPL~ A - E
86 parts by weight (abbreviated as parts hereinafter) of isopropyl alcohol
was charged into a four-neck flask installed with dispersing blades, a
thermometer and a reflux condenser and the 0.9 parts of azobis isobutyronitrile
as polymerization initiator, 1.0 parts of lauryl mercaptan, 1.0 parts of acetic
acid as pH adjuster were added thereto. Monomer raw materials composed of
ingredients shown in the following table 1 to 3 were charged into a dropping
funnel and then dropped at the refluxing temperature for isopropyl alcohol over
a period of 4 hours with dispersing in order to polymerize and further 0.1 parts
of azobis isobutyronitrile was added thereto for complete reaction for two hours.
And then 240 parts of water was charged thereto to dissolve resin uniformly, and
then isopropyl alcohol wa~ withdrawn at 65C under reduced pressure. Each liquid
containing a polymer thus obtained was uniform solution wherein the concentration
of the polymer was 30%, viscosity was 50 to 100 cps (BM type viscometer, 30C)
and pH was 3.5 to 4Ø
`:
WO 94/oo~o PCI/IJS93/05790 `
2 ~, ~ ,, r.~
Table 1
_
Example .:
_ 2--3--4--5 :~
Methyl chloride salt of dimethylamino- 5 _ 20 _ 75 ~
MonomerA component propyl methacrylamide _ ~
composition . .
Acetate of dimethylaminopropyl meth- _. 5 _ 20 _ .
acrytamide . _--
10(parts by 3-methacryloxypropyl trimethoxy silane 0.5 0.5 3 3 5
weight)B component vinyl trimethoxy silane _ _ _ . _ ~-:
. . ...
methyl methacrylate 49.5 49.5 32 32 _
Unsaturated . : . -
monomer butyl acrylate 20 20 20 20 20 M
,,.
2~thyl hexyl acrylate 20 20 20 20 _ ~
_ ,
styrene 5 5 5 5 ... ~
_ _ _ _
:
Table 2 j-~
_ ,
Example ; .,
_ ----7 --3 _ "~,~
Monomer Methyl chloride salt of dimethylamino- ._ 75 20 . .
CompositionA component propyl methacrylamide . . .
Acetate ot dimethylaminopropyl meth- 75 _ . 5 i~
(parts by acrylamide ._ ~
weight) 3-methacryloxy propyl trimethoxy 5 _ _ . !.
B component silane
_
vinyl trimethoxysilane _ 5 3 0.5 `
.~'
methyl methacrylate . _ 32 49.5 .
Unsaturated
monomer butyl acrylate 20 20 20 20
2-ethyl hexyl acrylate . _ 20 20 ':
. _ ,."
styrene _ . 5 5 ~:
. . ~
:
W094~00520 21 1 ~9~ ~ PCI/US93/05790 ~ ~
Tabb 3
Compara~ve E~amples
. . jExample
_ A E C D E - ;:
S A component Methyl chloridu salt ot dimethyl- 5 . 3 _ 2 :
Monomer aminopropyl methacrylamide :
Composition _
Acetate of dimethylaminopropyl _ 5 _ 3 _. ~ "
(parts by weight) methacrylamide
B component 3-methacryloxy propyl trimethoxy 0.3 0.3 0.5 0.5 ; ;:
_ _ _ '.~
vinyl ttimethoxysilane ~ _ _ 0.5 ; 0
_ _ . _ . ,.
monomer methyl methaclylate 49.7 49.7 51.5 51.5 51.5 ;
butyl acrylate 20 20 20 20 20
2-ethyl hexyl acryiate 20 20 20 20 20 ~ ~
_ , . .
styrene 5 5 5 5 5 , ~
_ _ _ . -,
All samples in these examples and comparative examples were applied to two
kinds of asbestos cement calcium silicate plates (one was pH of 9, the other was
pH of 7, specific gravity was 0.7 for both) at the ratio of 15~ concentration and
100 g/m2 and then let them alone to dry at room temperature for 7 days. Later,
the were divided into twenty five pieces of micro partition in 4mm x 4mmm wherein
gridiron pattern was made. After adhesive tape (Nichiban brand cellophane tape
of 24mm in width) was attached thereto and peeled off, the number of micro
partition remained on the part of basic materials was counted. Adhesive property
with primer layer and paint for finish surface was valued thereby. In addition,
all the samples were dipped into warm water of 60C for 7 days after drying prior
to dividing into partitions and then warm water resisting adhesion was valued in
the same method as above. As a result of the above adhesive test, the samples
with not less than 23 left adhered were represented as ~, the samples with 20 to
2Z as 0, the samples with 10 to 19 as ~, the samples with not more than 9 as
These results are shown in the following Tables 4 to 7.
Furthermore, all samples of the above examples and comparative examples
were applied to slate plates at the ratio of 15~ concentration and lOOg/m2 and
then left alone for drying at room temperature for 7 days. Later, waterproofing
test was performed in accordance with JISA-6910. Samples wherein volume of water
permeability one day after were not more than lcc were represented as ~, not more
than 3cc as 0, not more than 5cc as ~, not less than 5cc as ~. These results are
also shown in the following Tables 4 to 7.
WO 94/OOS20 PCr/US93/05790
21 15~
Table 4
. = Exa nple .
1 2 3 ~ 4
_ Adhes;on in normai
Asbestos cement calcium silicate plates (basic condition ___ ~ ..
material surtace layer pH = 9)
Adhesion in warm water ( ~) O (~) (3 ~ ,~
_ Adhesion in normal ~ __ .~
Asbestos cement calcium silicate plates (basic condition t,'
matetial sur1ace layer pH = 7)
Adhesion in warm water O O O ()
~,
Slate plates Waterproot (3 O ~)
Table
`:~
Example -~-
Adhesion in normal _ O O
Asbestos cement calcium silicate plates (basic condition r,-
material suttace layer pH = 9) ~^
Adhesion in warm water c~ O Q ~ ~
,.. .
Asbestos cement calcium silicate plates (basic Adhesion in normal (3 O (3 (3 ~-
material suttace layet pH = 7) condition _ .
Adhesion in warm water _ _ _ _ ~
Slate plates Waterproof ___ (3 ~.
2~5 .
Tabb 6
. ..
Example Coml arative ~Example
9 A B ¦ C :~
. Adhesion in normal O O :~
Asbostos cement calcium silicate plates (basic condition
material surtace layer pH = 9)
Adhesion in warm water C~) O O e
Asbestos cement calcium silicate plates (basic Adhesion in normal
material surface layer pH = 7) condition
. Adhesion in warm water (~ O O OE~ :.
Slate plates Waterproot ( ) O e e
W O 94/00~20 2 1 ~ i~9;~CT/US93/05790
~abk7 ~:
_ :.:
. Comparati ve Example .
.,:.
Asbestos cement calcium silicate plates (b~sic Adhesion in normal O O
material surtace layer pH - 9) condition ~:
Adhesion in warm water e e
..
Asbestos cement calcium silicate plates (basic Adhesion in normal O O
material surtace layer pH = 7) condition : .
_ _ .
_ Adhesion in warm water ~ _ ~)
Siate plates Waterproof ~ ~
From the results of the above Tables 4 to 7, it is found out that everysample6 of examples has superior properties compared with comparative examples.
EXAMPLES lO TO 12, COMPARATIVE EXAMPLE F
An emulsion polymer (emulsion A) was produced in the following composition,
and then mixed with the samples gained in the above example 2 in accordance with15 the composition of Table 8 shown later, so that aqueous liquid for primers was
obtained.
<Composition of Emulsion A>
Butyl acrylate 50 parts
: - Methyl methacrylate 48 parts
Dimethyl diallyl ammonium~chloride 2 parts
Emulgen 935 (Product of Kao) 4 parts
Water 156 parts !"'~
Ammonium persulfate 0.3 parts
<General Characteristic of Emulsion A>
Non-volatile re~idue 38.2%
Viscosity 200cps
pH 2.8
Lowest temperature for making film 5C
Next, as for aqueous liquid for primer obtained in the above method, the;~
characteristics (adhesive test in normal conditions and warm water, waterproofing
test) were valued in the same method of Example 1. The results were also shown
in the following Table 8.
11 '-`~
WO94/00520 21~ r!c~ PCT/US93/05790
Table 8 :~
_ . _ .
. E~ample Comparative :
1 0 11 1 2 Example , ~:
Aqueous liquid of 75 50 25 _ .
Mixture ot composition (parts by welght) Example 2 _ _ :.
Emulsion A 25 50 75 ~100 r ;:
! .' .
Pondage 150 125 100 100
Concentration (%) 1a8 19.6 20.5 19.0 ; i
Asbestos cement calcium silicate plates ~basic Adhesion in normal (3 (~) O ~8) .,
material surface layer pH= 9) condition
,~ .
Adhesion in warm C3 Q () ~ ~
water . ~.
_ _ ... j.
Asbestos cement calcium silicate plates (basic Adhesion in normal (~) (~) O (~)
material surface layer pH = 7) condition
Adhesion in warm C~ G(3 ~
.
SJat~ plates Waterproof O (~) C3
From the results of the above Table 8, it i5 found out that when an
unqoluble polymer emulqion waq qeparately produced, and then mixed with the
samples of the above examples, preferable liquid for primers can also be
obtained.
EFF15CTS OF l~E INVh~ION
Aqueous liquid for primers in the present invention contains a copolymer
composed of two kinds of ~pecial monomerq ~A component and B component) and an
ethylenic unsaturated monomer (C component) at a specific ratio, wherein a strong
coat superior in waterproof and alkali resistance property by crosslinking
reaction can be formed irrespective of the degree of alkali of basic materials.
In addition, resin in high concentration and low viscosity can be materialized
without deteriorating the speed of crosslinking reaction compared with prior
method, so that is has superior permeability to the basic materials, adequate
reinforce ability to basic materials and waterproof under high concentration
condition. Therefore, in spite of aqueous property, it shows a superior
reinforcing effect to basic materials, which is not less than that of prior
~olvent type primers, and furthermore, is safe and does not become a source for
- public nuisance. In addition, it shows affinity to paints for surface finish,
adhesives, or the like and has superior effects to strongly attach the finishing
layer comprising the above component on the surface of basic material.
- 12
